WO1990008181A1 - Verwendung von monocarbonsäurepolyoxyalkylester als schaumarme textilbehandlungsmitteln - Google Patents

Verwendung von monocarbonsäurepolyoxyalkylester als schaumarme textilbehandlungsmitteln Download PDF

Info

Publication number
WO1990008181A1
WO1990008181A1 PCT/EP1990/000012 EP9000012W WO9008181A1 WO 1990008181 A1 WO1990008181 A1 WO 1990008181A1 EP 9000012 W EP9000012 W EP 9000012W WO 9008181 A1 WO9008181 A1 WO 9008181A1
Authority
WO
WIPO (PCT)
Prior art keywords
monocarboxylic acid
acid
polyoxyalkylester
agents
aqueous
Prior art date
Application number
PCT/EP1990/000012
Other languages
German (de)
English (en)
French (fr)
Inventor
Ansgar Behler
Bernd Fabry
Bernd Wahle
Hildegard Von Delden
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to AT90900177T priority Critical patent/ATE86292T1/de
Priority to DE9090900177T priority patent/DE59000985D1/de
Priority to BR909007019A priority patent/BR9007019A/pt
Publication of WO1990008181A1 publication Critical patent/WO1990008181A1/de

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • the invention relates to the use of monocarboxylic acid polyoxyalkyl ester sulfonates as low-foaming wetting agents in aqueous alkaline treatment agents for textile fabrics.
  • wetting agents that are suitable for such alkaline treatment agents must be water-soluble and alkali-stable and must ensure uniform wetting of the goods.
  • wetting agents should be environmentally friendly, i.e. biodegradable and have no toxic effects on aquatic organisms.
  • defoamers for example silicones
  • the use of defoamers is not only with additional ones Cost associated, but often has undesirable side effects, such as uneven wetting of the textile fabrics, as well as silicone oil stains that are difficult to remove in the case of silicone-containing defoamers.
  • the object of the invention was therefore to develop silicone-free, low-foaming, liquid and thus directly meterable, water-soluble, alkali-stable and readily biodegradable wetting agents for textile fabrics or yarns which meet all of these product requirements in a uniform substance.
  • the invention is based on the surprising finding that the high demands placed on wetting agents by monocarboxylic acid polyoxyalkyl ester sulfonic acids in the form of their alkali metal, ammonium and / or amine salts.
  • the invention accordingly relates to the use of alkali metal, ammonium and / or amine salts of carboxylic acid polyoxyalkyl ester sulfonic acids, prepared by reacting monounsaturated monocarboxylic acid polyoxyalkyl esters of the general formula in which R is an alkyl radical with 1 to 22 C atoms or an alkenyl radical with 3 to 22 C atoms, m is a number from 10 to 21, n is 2 and / or 3 and x is a number from 1 to 20, with Sulfur trioxide and subsequent reaction of the sulfonated monocarboxylic acid polyoxyalkyester obtained with aqueous alkalis as low-foaming wetting agents in aqueous alkaline treatment agents for textile fabrics or yarns.
  • R is an alkyl radical with 1 to 22 C atoms or an alkenyl radical with 3 to 22 C atoms
  • m is a number from 10 to 21
  • n is 2 and / or 3
  • the salts of monocarboxylic acid polyoxyalkyl ester sulfonic acids can be prepared in a manner known per se in which monounsaturated monocarboxylic acid polyoxyalkyl esters are sulfonated at temperatures between 5 and 120 ° C. with sulfuric acid, oleum, chlorosulfonic acid or SO 3 -containing gas mixtures.
  • the sulfonations of monounsaturated monocarboxylic acid polyoxyalkyl esters according to DE 37 20 000 are preferably carried out at temperatures between 5 and 100 ° C. using gas mixtures of SO 3 and air or inert gases, for example nitrogen, in which the SO 3 content is between 1 and 10% by volume, carried out.
  • the sulfonation temperatures are particularly preferably between 5 and 40 ° C.
  • the molar ratio of monounsaturated monocarboxylic acid polyoxyalkyl esters: SO 3 is about 1: 1.
  • the sulfonations are carried out continuously or batchwise in conventional reactors suitable and customary for the sulfation of fatty alcohols or for the sulfonation of fatty acid esters, alkylbenzenes or olefins, preferably of the type of falling film reactor (see, for example, in Kirk-Othmer: Encyclopedia of Chemical Technologie 22, 28 ff (1983)).
  • the sulfonation product obtained is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, in which the sulfonated reaction mixture is preferably added to the aqueous solution.
  • 1 to 1.2 moles of hydroxides and / or amines are used per mole of sulfur trioxide added.
  • Excess hydroxide and / or amine is required to neutralize the gaseous SO 3 dissolved in the sulfonation product.
  • Sodium hydroxide, potassium hydroxide, diethanolamine and / or triethanolamine, particularly preferably sodium hydroxide, are preferably used as neutralization bases.
  • the concentration of the hydroxides and / or amines in water is preferably chosen so that the end product forms a low-viscosity solution.
  • the reaction product also contains sultones.
  • the formation of sultons is a known reaction in the sulfonation of olefinic double bonds.
  • hydrolysis in which the reaction products are heated until the sultone groups formed have been completely destroyed while maintaining a pH of 7 by controlled addition of alkali metal hydroxide become.
  • the time required for this is dependent on pressure and temperature. For example, at boiling temperature under normal pressure, complete hydrolysis can be achieved in 4 to 6 hours, under pressure at higher temperatures, but in a considerably shorter time.
  • the alkoxylations of the alcohols with ethylene oxide and / or propylene oxide are carried out using known industrial processes carried out (see, for example, in Chemische Technologie, Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Kunststoff (1986)).
  • the average degree of oxalkylation x of the mixtures of homologous oxalkylates obtained corresponds to the molar amount of the alkylene oxides attached and is between 1 and 20, preferably between 2 and 10.
  • oxyalkylated alcohols obtained are then reacted with C 11-22 monounsaturated monocarboxylic acids in a manner known per se in the presence of esterification catalysts, for example tin grinding.
  • Suitable monounsaturated monocarboxylic acids with 11 to 22 carbon atoms are, for example, 10-undecenoic acid, palmitoleic acid, oleic acid, petroselinic acid, elaidic acid and / or erucic acid.
  • oleic acid and / or erucic acid are used in pure form or in the form of fatty acid mixtures rich in oleic acid and erucic acid, as can be obtained from fats of animal and / or vegetable origin.
  • Preferred monocarboxylic acid polyoxyalkyl esters are those of the general formula
  • R represents an alkyl radical having 8 to 18 carbon atoms, m 17 and / or 21, n 2 and / or 3 and x is a number between 2 to 10.
  • the wetting agents to be used according to the invention are light yellow to light brown, clear, aqueous, alkaline solutions. If desired, these can be bleached with hydrogen peroxide solutions or alkali hypochlorite solutions (chlorine solution) in a manner known per se at temperatures between 40 and 55 ° C. For stabilization against bacterial attack, preservation with preservatives known from the prior art, for example p-hydroxybenzoate and / or sorbic acid, is recommended.
  • the active substance content of monocarboxylic acid polyoxyalkyl ester sulfonate salts in the solutions is between 10 and 50% by weight.
  • Monocarboxylic acid polyoxyalkyl ester sulfonate salt-containing wetting agents are distinguished by a particularly low foaming power. This is of particular advantage in strongly alkaline treatment agents, for example in alkaline cold bleaching liquors, hot bleaching liquors, mercerizing liquors, alkaline boiling-off and degreasing agents, since such alkaline treatment agents have a particular tendency to form foam.
  • the monocarboxylic acid polyoxyalkyl ester sulfonate salts are preferably used as low-foaming wetting agents in aqueous alkaline bleaching liquors. These contain hydrogen peroxide or compounds which form hydrogen peroxide in aqueous solution as a bleaching agent.
  • the pH of the bleaching baths is adjusted to 10 to 14 with strong bases, for example with NaOH and / or KOH.
  • the known anionic and nonionic wetting agents for example alkyl sulfates, sulfonates, carboxylates, phosphates and / or alkylpolyoxyethylene glycol ethers, which are stable and effective in these media, tend to produce a lot of foam in the high-speed apparatus.
  • foam damping agents for example silicone oils
  • the salts of monocarboxylic acid polyoxyalkyl ester sulfonic acids to be used according to the invention develop practically no foam in such baths, so that the addition of defoamers is unnecessary.
  • the bleaching liquors containing 10 to 100 ml of hydrogen peroxide, 35% by weight, 5 to 20 g of bases from the group of sodium or / or potassium hydroxide, 5 to 50 ml of stabilizers, for example sodium water glass (Na 2 O: SiO 2 1: 2; 38 - 40 oBe) and / or alkali salts of ethylenediaminetetraacetic acid and / or polyphosphates, 0.1 to 1.0 g of magnesium salts, for example magnesium sulfate, 0.5 to 10 g of sequestering agent, for example Securon R 540, Henkel KGaA and 0.3 to 30 g, based on the active substance, of monocarboxylic acid polyoxyalkyl ester sulfonate salts, are applied to fabrics or yarns at temperatures between 15 and 90 ° C, preferably at a temperature of about 20 ° C (cold bleach).
  • the cotton-containing textile fabrics such as woven and / or knitted fabrics, which are preferably treated with bleaching liquors containing monocarboxylic acid polyoxyalkyl sulfonate salt, and yarns are distinguished by good degrees of whiteness and good hydrophilic properties.
  • EO means ethylene oxide
  • the acidic reaction mixture was cooled to 10 ° C and bleached in portions with 5% by weight of a 35% by weight hydrogen peroxide solution, the temperature of the mixture also being kept below 60 ° C by cooling.
  • the bleached product was then stirred into a solution of 48 g (1.2 moles) of NaOH in 250 ml of water and hydrolyzed at 95 ° C for 4 hours to separate the product.
  • the upper phase (approx. 10% by weight), which contained unsulfonated product, was separated off.
  • the lower phase containing oleic acid-ethyl ester sodium sulfonate was adjusted to a pH of 7 with mineral acid.
  • Oleic acid oleylester 300 96> 300> 300 104 135 sodium sulfonate
  • the bleaching liquors were treated with oleic acid 2.9E0 decyl ester sodium sulfonate, prepared according to Example 1.1, and for comparison oleic acid oleyl ester sodium sulfonate, prepared according to example 1.2, or oleic acid 2.9E0 decyl ester as wetting agent in different Amounts added.
  • the wetting effect of these liquors was determined at 20 ° C. in accordance with DIN 53 901 (determination of the immersion wetting power of surfactant solutions). The following network times were obtained:
  • the foaming behavior of the cold bleaching solutions (composition analogous to 2.b)), the wetting agent 2.4 g AS / l cold bleaching liquor oleic acid 2.9E0 decyl ester sodium sulfonate and for comparison 2.4 g AS / 1 cold bleaching liquor oleic acid oleylester sodium sulfonate or 2.4 g AS / l cold bleaching liquor containing oleic acid 2.9E0 decyl ester was checked at 20 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP1990/000012 1989-01-12 1990-01-04 Verwendung von monocarbonsäurepolyoxyalkylester als schaumarme textilbehandlungsmitteln WO1990008181A1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT90900177T ATE86292T1 (de) 1989-01-12 1990-01-04 Verwendung von monocarbonsaeurepolyoxyalkylester - sulfonaten als schaumarme textilbehandlungsmittel.
DE9090900177T DE59000985D1 (de) 1989-01-12 1990-01-04 Verwendung von monocarbonsaeurepolyoxyalkylester -sulfonaten als schaumarme textilbehandlungsmittel.
BR909007019A BR9007019A (pt) 1989-01-12 1990-01-04 Aplicacao de esteres polioxialquilicos de acidos monocarboxilicos como agentes de tratamento de texteis pouco espumantes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3900699A DE3900699A1 (de) 1989-01-12 1989-01-12 Verwendung von monocarbonsaeurepolyoxyalkylester-sulfonaten als schaumarme netzmittel in waessrigen alkalischen behandlungsmitteln fuer textile flaechengebilde
DEP3900699.9 1989-01-12

Publications (1)

Publication Number Publication Date
WO1990008181A1 true WO1990008181A1 (de) 1990-07-26

Family

ID=6371922

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/000012 WO1990008181A1 (de) 1989-01-12 1990-01-04 Verwendung von monocarbonsäurepolyoxyalkylester als schaumarme textilbehandlungsmitteln

Country Status (7)

Country Link
US (1) US5250076A (pt)
EP (1) EP0453447B1 (pt)
JP (1) JPH04502651A (pt)
BR (1) BR9007019A (pt)
DE (2) DE3900699A1 (pt)
ES (1) ES2054330T3 (pt)
WO (1) WO1990008181A1 (pt)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010558A1 (de) * 1990-12-10 1992-06-25 Henkel Kommanditgesellschaft Auf Aktien Teppichreinigungsmittel
WO1993025646A1 (en) * 1992-06-17 1993-12-23 Lion Corporation Detergent composition having low skin irritability
EP4365158A1 (en) 2022-11-04 2024-05-08 PCC ROKITA Spolka Akcyjna Method of selective paradichlorobenzene preparation with improved catalytic system recovery

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417708A (en) * 1994-03-09 1995-05-23 Cook Incorporated Intravascular treatment system and percutaneous release mechanism therefor
US5968370A (en) * 1998-01-14 1999-10-19 Prowler Environmental Technology, Inc. Method of removing hydrocarbons from contaminated sludge

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197974A1 (pt) * 1972-09-02 1974-03-29 Henkel & Cie Gmbh
CH610209A5 (en) * 1976-04-26 1979-04-12 Ciba Geigy Ag Wetting agent and foam inhibitor based on anionic surfactants
DE3720000A1 (de) * 1987-06-15 1988-12-29 Henkel Kgaa Fettsaeurepolyoxyalkylester-sulfonate, verfahren zu ihrer herstellung und ihre verwendung als tenside

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1000328A5 (fr) * 1987-02-19 1988-10-25 Interox Sa Particules de composes peroxygenes stabilisees, procede pour leur fabrication, et compositions en contenant.
US4963157A (en) * 1987-04-17 1990-10-16 Nippon Peroxide Co., Ltd. Method for bleaching cellulosic fiber material with hydrogen peroxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2197974A1 (pt) * 1972-09-02 1974-03-29 Henkel & Cie Gmbh
CH610209A5 (en) * 1976-04-26 1979-04-12 Ciba Geigy Ag Wetting agent and foam inhibitor based on anionic surfactants
DE3720000A1 (de) * 1987-06-15 1988-12-29 Henkel Kgaa Fettsaeurepolyoxyalkylester-sulfonate, verfahren zu ihrer herstellung und ihre verwendung als tenside

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 92, no. 18, 05 Mai 1980 Columbus, Ohio, USA & al.: "Antifrothing agent& SU,A,0707591 siehe Zusammenfassung *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992010558A1 (de) * 1990-12-10 1992-06-25 Henkel Kommanditgesellschaft Auf Aktien Teppichreinigungsmittel
US5429684A (en) * 1990-12-10 1995-07-04 Henkel Kommanditgesellschaft Auf Aktien Water-based carpet cleaning composition and method
WO1993025646A1 (en) * 1992-06-17 1993-12-23 Lion Corporation Detergent composition having low skin irritability
US5681803A (en) * 1992-06-17 1997-10-28 Lion Corporation Detergent composition having low skin irritability
EP4365158A1 (en) 2022-11-04 2024-05-08 PCC ROKITA Spolka Akcyjna Method of selective paradichlorobenzene preparation with improved catalytic system recovery

Also Published As

Publication number Publication date
EP0453447B1 (de) 1993-03-03
ES2054330T3 (es) 1994-08-01
EP0453447A1 (de) 1991-10-30
US5250076A (en) 1993-10-05
JPH04502651A (ja) 1992-05-14
DE59000985D1 (de) 1993-04-08
BR9007019A (pt) 1991-11-12
DE3900699A1 (de) 1990-07-19

Similar Documents

Publication Publication Date Title
EP0301414A2 (de) Oberflächenaktive Hydroxysulfonate
EP0174610B1 (de) Verwendung von Ethersulfonaten als schaumarme Netzmittel in wässrigen, sauren und alkalischen technischen Behandlungsmitteln
DE3918252A1 (de) Fettalkylsulfate und fettalkyl-polyalkylenglycolethersulfate, verfahren zu ihrer herstellung und ihre verwendung
EP0137983B1 (de) Ethersulfonate und ihre Herstellung
EP0355613B1 (de) Verwendung von Mischungen, enthaltend (A) Alkali-, Ammonium-und/oder Aminsalze sulfonierter, ungesättigter Fettsäuren und (B) alkoxylierte Alkylalkohole als Netzmittel
DE4137317A1 (de) Ester von fettsaeuren mit ethoxylierten polyolen
EP0696661A1 (de) Multifunktionelle Textilhilfsmittel-Zusammensetzungen
EP0295535A1 (de) Fettsäurepolyoxyalkylester-sulfonate, Verfahren zu ihrer Herstellung und ihre Verwendung als Tenside
EP0082823B1 (de) Verfahren zum Bleichen von Fasermaterialien unter Verwendung von Oligomeren von Phosphonsäureestern als Stabilisatoren in alkalischen, peroxydhaltigen Bleichflotten
EP0453447B1 (de) Verwendung von monocarbonsäurepolyoxyalkylester -sulfonaten als schaumarme textilbehandlungsmittel
WO1991009926A1 (de) Flüssiges reinigungsmittel für harte oberflächen
EP0394848A1 (de) Netzmittel für alkalische Textilbehandlungsmittel
US1935264A (en) Esters of sulphonated aromatic carboxylic acids and peocess of making same
EP0382093A1 (de) Färbereihilfsmittel
DE4003096A1 (de) Sulfierte hydroxycarbonsaeureester
EP0626944B1 (de) Thiodiglykol-derivate, verfahren zu ihrer herstellung und deren verwendung zum weichmachen von textilien
DE4332187A1 (de) Stickstofffreie anionaktive Avivagemittel
DE3941061A1 (de) Fettsaeuresorbitanestersulfate
DE4300935A1 (de) Sulfonierte Diester
DE702229C (de) Verfahren zum Reinigen von Textilgut
DE4316214A1 (de) Sulfonierte Diester
DE4432363A1 (de) Verfahren zur Hersellung von Äpfelsäurediestersulfaten
DE19719688A1 (de) Netzmittel zur Verwendung in wäßrigen Behandlungsbädern für textile Fasermaterialien
DE1283227B (de) Verfahren zur Herstellung von Olefinsulfonaten
DE4331294A1 (de) Reinigungsmittel für harte Oberflächen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): BR JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1990900177

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1990900177

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1990900177

Country of ref document: EP